Process for the dyeing, padding and printing of polyester fibers



United States Patent 3,l22,4lll

Patented Feb. 25, 1984 Free 3,122,410 PRGCEEfi FGR THE DYEEWG, PADDKNGAND PRINTENG @F PGLYESTER FEBERS (Zurt lliuelier, Basel, and Urs Lerch,Neu-Allschwil, Switzerland, assignors to Sender; Ltd, Basel, SwitzerlandNo Drawing. Filed .lune 23, 1961?, Ser. No. 38,1ll3 Claims priority,application Switzerland lady I, 59 6 Claims. (ill. 84l) It has beenfound that dyestuffs of the formula N O 1 Z (Y)!!! (U) n (I) wherein arehighly suitable for the dyeing, padding and printing of polyesterfibers. They give red, violet or blue shades which possess very goodfastness properties, in particular fastness to li ht, washing,perspiration, sea water, gas fumes, sublimation, pleating, steaming andpressing. it is surprising that light-fast dyeings should be obtained intlu's way, for monoazo dyestuffs from l-diazo-Z-nitrobenzenes andtertiary couplable amines have not proved successful for dyeingcellulose acetate because of their insufiicient fastness to light. Theblue dyestuffs of this series are particularly suitable as main elementsfor navy blue and black combinations.

The dyestulfs of the invention reserve wool, cotton and viscose inblended fabrics. This property has become of great importance owing tothe wide variety of blended fabrics now produced, especially thosecomposed of a polyester fiber and wool. When blended fabrics of thistype are dyed with disperse dyestulfs the wool is stained to aconsiderable depth and as the stain is not fast the goods lose in value.There are no commercially available bluish red, violet and blue dispersedyestutls which give a sufilciently good reserve or" wool.

Up to the present no blue azo dyestuffs have been known which can beused for dyeing polyester fibers. The dyestufis of this invention thusunexpectedly fulfill a technical purpose and moreover are inexpensiveand dischargeable. They are particularly valuable for combination withsmall amounts of suitable red components for the production ofinexpensive navy shades of good fastness to light, washing,perspiration, chlorine, sublimation, pleating and heat setting, and withsuitable red and yellow components for blacks of similarly goodfastness. The blue disperse dyestufts of the anthraquinoid series whichare employed are not dischargeable and hence give a poorer reserve ofwool. The anthraquinoid dyestuffs used possess good building-upproperties but are not sufficiently fast to sublimation, pleating andheat-setting, while those which are superior in these properties possesspoor building-up properties and are therefore uneconomical for navy blueand black mixtures. in fact, all the mixtures that have yet beenmarketed are insufiiciently fast to sublimation, pleating andheat-setting, and comparatively expensive.

A further object of this invention is a process for the production ofstable dyeing preparations, which is characterized by mixing 55 to partsof one or more dyestuffs of the general formula O2N i i=r I N 2 X NHCORa (II) wherein X represents hydrogen, chlorine, bromine, cyano,trifiuoromethyl or nitro,

Z hydrogen or low molecular alkoxy,

R low molecular alltyl, low molecular alltoxyalkyl or low molecularacyloxyalkyl,

R low molecular acyloxyalkyl, and

R low molecular alkyl,

and 45 to 5 parts of one or more dyestuffs of the general formula (III)wherein V represents hydrogen, chlorine or bromine,

W chlorine, bromine, cyano or trifluoromethyl, and 3,; hydrogen, methyl,ethyl or chlorine, and

R possesses the aforecited meaning,

with one or more of the anionic dispersing agents or standardizingagents commonly used in disperse dyestuffs.

The invention further comprehends a process for the dyeing, padding andprinting of polyester fibers with disperse dyestulfs, which ischaracterized by the use for this purpose, either simultaneously orsuccessively in any order, of 55 to 95 parts of one or more dyestuffs ofthe general Formula II and 4-5 to 5 parts or one or more dyestuffs ofthe general Formula ill.

In this way it is possible for the first time to dye polyester fibersinexpensively in navy blue shades and blacks which possess good fastnessto light, perspiration, washing, sublimation, leating and heat-setting.

The term polyester fibers is used here to cover the condensationproducts of terephthalic acid and ethylene glycol marketed under theregistered trademarks Terylene, Dacron, Dralon, Tergal, Terital, Treviraand Diolen, and similar fibers such as Kodel which is stated to be acondensation product of terephthalic acid and1,4-bis-(hydroxymethyl)-hexahydrobenzene.

The dyestuffs are dyed by the known methods, either with carrier attill- C. or without carrier at 199- C. under pressure. Additions ofdispersing agents can be beneficial. Printing and padding are bestcarried out in presence of suitable thickening agents, followed byfixation at high temperature with or without steam. -The dyestufis usedin the process are produced by the known methods by diazotization ofl-amino-ZA-diuitrb benzene and its derivatives, e.g. in nitrosylsulfuricacid, and coupling with an amine of the formula wherein U, X, Y, Z, mand n possess the aforementioned mean- H108 R d enotes low molecularalkyl, low molecular alkoxyalkyl, low molecular hydroxyalkyl or, when mis and n is 1, low molecular cyanoalkyl and R low molecularhydroxyalkyl, with functional derivatives of aliphatic carboxyiic acids,if necessary in presence of an acid-binding agent and/or a diluent whichdoes not influence the reaction. It is often of advantage to increasethe temperature. The monoazo dyestuffs thus obtained are isolated by oneof the standard basic operations, e.g. filtration, evaporation of thesolvent and filtration, distillation of solvent and filtration,precipitation from solvent with a suitable agent and filtration.

The further treatment of the monoazo dyestuffs to give dyestufipreparations can be carried out in several ways. For example, the drydyestuif can be ground with a suitable dispersing agent, if desired inpresence of fillers, or kneaded in paste form with a dispersing agentand subsequently dried with vacuum or in a nozzle drier.

The dyestuffs can be dyed, padded or printed in mixture with each otheror with other suitable polyester dyestuffs.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade. Example 1 7 parts of2.4-dinitro-6-bromo-2'-acetylamino-4-bis- (acetoxy-ethyl)-amino--ethoxy-1.1-azobenzene (melting point 138), 4 parts of sodiumdinaphthylmethanedisulfonate, 4 parts of sodium cetylsulfate and 5 partsof anhydrous sodium sulfate are ground in a ball mill for 48 hours togive a line powder.

1 part of this powder is pasted and dispersed with a little water andthe suspension run through a sieve into a dyebath containing 0.5 g./l.lauryl alcohol sulfonate (liquor ratio 1:40). The liquor ratio may varywithin wide limits. 100 parts of a scoured fabric of Dacron (registeredtrademark) polyester fiber are entered at 40- 50", the bath slowlyheated to 95-100 and dyeing continued at this temperature for 1-2 hoursin presence of 5 cc./l. of an aqueous emulsion of a chlorinated benzene.The fabric is subsequently rinsed, soaped, rinsed again and dried. It isdyed a greenish blue shade which is fast to light, cross dyeing,washing, water, sea water, perspiration, gas fumes, sublimation, heatsetting and pleating, and is white dischargeable.

In place of 100 parts of Dacron, an equal weight of one of the polyesterfibers Terital, Dralon, Trevira or Kodel can be dyed in the same way ingreenish blue shade which possesses the same good fastness properties.

Example 2 parts or" 2.4-dinitro-6-bromo-2-propionylamino-4'-bis-(acetoxyethyl)-amino-1.1'-azobenzene (melting point 118-120"), 10parts of sulfite cellulose waste powder and parts of water are ground inthe wet state in a ball mill for 48 hours and the resulting paste driedin a nozzle drier. A dyebath is prepared with 1 part of this dyestufipreparation and 1000 parts of water. parts of a scoured fabricrofTerylene (registered trademark) are entered at 40-50", the dyebathheated slowly to and dyeing continued for about 30 minutes at thistemperature under pressure, with subsequent rinsing, soaping, rinsingand drying. The fabric is dyed a violet shade showing similar fastnessproperties to that of the dyestuii of Example 1.

Example 3 10 parts of 2.4-dinitro-6-bromo-2'-acetylamino-4-bis-(acetoxy-ethyl)-amino-5-methoxy-1.1-azobenzene (melting point 123) inthe form of the moist undried filter press cake, 10 parts of Turkey redoil and sur'ficient water to give a total of 200 parts are mixedtogether to form a paste. After two hours a dyebath is set with 5 partsof this paste, 5 parts of 2-hydroxy-1.1-diphenyl and 2000 parts or"water. 100 parts of Tergal (registered trademark) polyester fiber areentered in the bath and dyed for 1 hour at the boil, rinsed and dried. Ablue, well penetrated dyeing with excellent fastness properties isobtained.

Example 4 7 parts of 2.4-dinitro-6-bromo-2'-methyl-4'-(N-ethyl-N-acetoxyethyl)-amino-1.1'-azobenzene (melting point 134-136"), 38 partsof sodium dinaphthylmethanedisulfonate and 530 parts of water are groundin a ball mill for 48 hours. The colloidal solution formed is mixed with25 parts of butylcarbitol and 400 parts of 6% carboxymethylcellulose.This printing paste is highly suitable for vigoureux or melange printingon slub'bing of polyester fiber, e.g., Diolen (registered trademark). Itis applied from two rollers at a coverage of 78% and the slubbing issteamed at 115-120" without intermediate drying. Brownish red prints ofvery good fastness are obtained.

Example 5 A finely dispersed aqueous suspension of 17 parts of2.4-dinitro-6-bromo 2'-methyl 4 (N cyanoethyl N-et-hyl)-amino-1.1'-azobenzene (melting point 188-190), 48 parts ofsodium dinaphthylrnethanedisulfonate and 25 parts of butyl carbitol in50 parts of water is mixed with 500 parts of crystal gum 1:2, 30 partsof glycerine and 320 parts of water. The paste formed is printed on afabric of polyester fiber, steamed at 7 to 10 lb. per sq. in. pressureto develop the shade, and then rinsed, soaped and dried. A sharp-edgedred print with outstanding fastness properties is obtained. Similareffects are obtained when the dyestufl? used in this example is dyed asdescribed in Example 2 and the dyeing discharged according to the methodgiven in SVF-Fachorgan 11, 620-621 (1956).

Example 6 A finely dispersed aqueous suspension of 15 parts of2.4-dinitro 2-propionylamino 4 bis (acetoxyethyl)- amino-1.1-azobenzene(melting point 35 parts of sodium dinaphthylmethanedisulfonate and 2parts of alginate is mixed with 1000 parts of water. A polyester fiberfabric is padded with this liquor by the normal procedure at atemperature between 20 and 70, air-dried at 60100, fixed by 30-90seconds treatment in dry air at -220, rinsed and soaped. A level, bluishred dycing with good fastness properties is obtained.

In the following tab-1e further dyestuffs suitable for dyeing, paddingand printing polyester fibers by the processed described herein arelisted; they are characterized by their melting points and their shadeson Dacron polyester fiber.

Exam- Melting Shade on Polyple No X Y U Z R R Point, ester Fiber deg.

NH-C OCH; ()CzH 2cetoxyethyl acetoxyethyL. 167 greenish blue. NH-COCH3-OCH3 d d0 160 D0. NHC O-CzH H 100 violet. NHCOCH; OCHa.- 136 grennishblue. CL NHOOCH3-. OCzH5 153 D0. 12 CN NHCOC;H H 159 D0. 13 CN Fl 7 FTdo eyanoetliyl 166 bluish red. 14 CN H H ethyl.-. do 180 violet. 15 CN-CH; H do do 179 reddish blue. 16"-.. CN CF H do aeetoxyethyln 102 blue.

Example 17 64 parts of a dyeing preparation prepared as described in thefirst paragraph of Example 1, 22 parts of a corresponding dyeingpreparation from the dyestufi 2-chloro- 4-nit-ro-4-(N-acetoxyethyl-Ncyanoethyl) amino 1.1-

azobenzene and 14 parts of a corresponding dyeing preparation from thedyestutf2.6-dichloro-4-nitro-4-(N-acetoxyethyl-N-cyanoethyl)-amino-l.1'-azobenzeneare intimately mixed. 8.7 parts of the mixture are pasted with a littlewater, and the suspension formed is added through a sieve to a dyebathcontaining 0.5 gram per liter of lauryl 25 alcohol sulfate (liquor ratio1:40); The liquor ratio may vary Within wide limits. 100 parts of ascoured fabric of Dacron polyester fiber are entered at -50, the bathheated slowly and dyeing continued for 1-2 hours at 95-100" in presenceof 5 cc. per liter of an 30 emulsion of a chlorinated benzene in Water.

The full black dyeing obtained is rinsed, soaped, rinsed and dried. Itis fast to light, cross dyeing, washing, water, sea water, perspiration,gas fumes, sublimation, heat-setting and pleating, and is whitedischargeable.

Example 18 3.6 parts of a dyeing preparation prepared according toExample 2 from the dyestuif 2.4-dinitro-6-chloro- 2 propionylamino 4 bis(acetoxyethyl) amino 5 methoxy-1.1-azobenzene and 0.4 part of a dyeingpreparation also prepared according to Example 2 from the dyestuff2-chloro-4-nitro-4-(N-acetoxyethyl-N cyanoethyl)- amino-1.1'-azobenzene,are added to 1000 parts of Water.

100 parts of a scoured fabric of Terylene polyester fiber are entered inthis dyebath at 40-50", the temperature slowly increased and dyeingcontinued for 30 minutes at 120-130 under static pressure. The fabric issubsequently rinsed, soaped, rinsed and dried. It is dyed a greenishnavy blue shade which has similar fastness properties to the dyeingproduced with the stable dyeing preparation of Example 17.

When 4 parts of a dyeing preparation prepared according to Example 2from the dyestufi 2..4-dinitro-6-bromo- 2-acetyl-amino 4'-bis(acetoxyethyl) amino 5' methoxy-1.l-azobenzene and 0.4 part of one alsoproduced according to Example 2 from the dyestufi 2-cyano-4-nitro-4-(N-acetoxyethyl N cyanoethyl) amino-1.1'-azobenzone are used, reddishnavy blue dyeings are obtained.

Example 19 A dyebath is prepared on the winch with 3.7 parts of a fnelydispersed preparation of 27 parts of the dyestuif- 2.4-dinitro-6bromo-2@acetylamino 4-bis-(acetoxyethyl) amino-5-ethoxy-1.1-azobenzene,3 parts of the dyestuif 2-cyano-4-nitro-4-(N-ethyl Ncyanoethyl)-arnino-1.1' azobenzene and parts of sodiumdinaphthylmethanesulfonate, mixed in the usual manner with 20 parts of astable emulsion of 2-hydroxy-1.1-diphenyl, e.g. as marketed under thename Carolid, in 10,000 parts of water. 200 parts of a blended fabric of55% Dacron and 5 45% wool are dyed in this bath for 1% hours at 95-98".

The Dacron is dyed in a reddish navy blue shade fast to light, crossdyeing, washing, water, sea water, perspiration, gas fumes, sublimation,heat-setting and pleating, while the wool component after intermediateclearing with hydrosulfite is unstained and can be dyed with suitabledyestuffs, e.g. prernctallized dyestuffs. The excess2-hydroxy-1.1'-diphenyl is removed from the goods by washing or heattreatment.

In the following table are listed further dyestufi mixtures consistingof dyestuffs of Formulas II and III. The symbols X, Z, R R R and W havethe meanings assigned to them in the introduction. The parts by weightof the two dyestuffs used for each mixture are given in separatecolumns, and in the last column the shade of the mixture on polyesterfiber is noted.

Dyestufi of formula (II) Dyestufi of f rrnula (III) V=H Shade ofdye-Example ing or print of mixture on polyester Parts X Z R] R2 R3 Parts R1R4 W fiber 95 CN H methyl aeetlrl xymethyl 5 methyl able-r0-.- brcm0navy blue.

at yl 55 00113..- ethyl acetoxy-1 do 45 butyl metl1yl CN Do.

D DY 80 NO: H acetexyacetnxyethyl 20 propyl ethyl Do.

ethyl. ethyl. ehler0- OCH3 butyl do methyl 25 butyl methyL--- Do. 95brom0 OCzHs methoxydo do 5 aeetoxy- H Do,

ethyl. ethyl. OF: OCaH5 niethoxyacetoxydo 20 acetoxy- Do,

propyl. propyl. propyl. 90 chl0r0 OCHa ethoxy acetoxydo 10 acctoxy- D0.

ethyl. ethyl. ethyl br01n0 OCH5 propicnylprcpionyldo 15 ethyl Do.

oxyethyl. oxycthyl. CF; OCHs. acetoxyaeetoxydo 10 propicnyl- Do.

ethyl. ethyl oxyethyl. 75 ehloro- OCH= propyl do pr0pyl- 25 methoxy- CND0.

ct lyl. 90 CF; 00 215.-.- ethyl acetcxymethyL..- 10 acgtotxyibromo Do.

u y 60 chl0ro OCHa 10 acetoxy- H Cl D0. 30 brorn0 OCZH5 ethyl. 2O ehlcro0011i.-. 25 d 20 bromo OCzH5 1O 25 (i0 002115..

7 Having thus disclosed the invention, What We claim is: 1. Process forcoloring linear polyester fibers comprising dyeing said fibers withdyestuff of the formula wherein R is a member selected from the groupconsisting of (lower) alkyl and (lower) acyloxyalkyl,

X is a member selected from the group consisting chlorine and bromine,

Z is a member selected from the group consisting hydrogen and(lower)-alkoxy, and

Y is a member selected from the group consisting (lower) alkyl and(lower)acylzunino.

2. A process for coloring linear polyester fibers comprising paddingsaid fibers with a dyestuff as defined in claim 1.

3. A process for coloring linear polyester fibers comprising printingsaid fibers with a dyesturf as defined in claim 1.

4. Polyester fibers colored with a dyestuif of the formula as defined inclaim 1.

5. Composition of matter consisting essentially of 55 to 95 parts ofdyestufi of the formula wherein R is a member selected from the groupconsisting of (lower)alkyl and (lower)acyloxyalkyl, R is (lower) alkyl,

X is a member selected from the group consisting of chlorine andbromine,

Z is a member selected from the group consisting of hydrogen and(lower)alkoxy, and

Y is a member selected from the group consisting of (lower)alkyl and(lower)acylamino and to 5 parts of dyestutf of the formula wherein V isa member selected from the group consisting of hydrogen, chlorine andbromine, W is a member selected from the group consisting of chlorine,bromine, cyano and trifiuoromethyl, R is a member selected from thegroup consisting of hydrogen, methyl, ethyl and chlorine, and R is amember selected from the group consisting of (1ower)alkyl,(lower)alkoxyalkyl and (lower)acyl oxyalkyl, with at least one anionicdispersing agent and at least one standardizing agent.

6. Polyester fibers colored with a dycstuff mixture of claim 5.

References Cited in the file of this patent UNITED STATES PATENTS2,173,417 Huber Sept. 19, 1939 2,312,398 Felix Mar. 2, 1943' 2,638,403Stead et al. May 12, 1953 2,726,237 Towne et al. Dec. 6, 1955 2,782,187Sartori Feb. 19, 1957 2,888,450 Kruckenberg May 26, 1959 3,042,478Merian et al. July 3, 1962 3,050,516 Merian et a1 Aug. 21, 1962

1. PROCESS FOR COLORING LINEAR POLYESTER FIBERS COMPRISING DYEING SAIDFIBERS WITH DYESTUFF OF THE FORMULA